Photographic layers suitable for the silver dyestuff bleaching method



United States Patent ice W Patented Apr. 13, 1965 3 178 290 in which X and Y have the above meanings, with a mono- PHGTQGRAPHIC is SUITABLE FQR THE hydroxynaphthalene monosulfonic or disulfonic acid SILVER DYESTUFF BLEACHING METHQD capable of coupling in a position vicinal to the hydroxyl Walter Anderau, Munchenstein, Switzerland, assignor to group, a reducing the resulting nitro-azo-dyestutf to the Ciba Limited, Basel, Switzerland,acompany of Switzer- 5 amino-azo-dyestuif, and, if desired, acylating the latter land y with a nitribenzoyl halide, such as metaor preferably g i 3 1 para-nitrobenzoyl chloride, reducing the nitro group to Claims Prlonty, P1 Jag Es an u y the amino group, and finally converting the amino-azo- Cl 9 (Cl dyestufi into a urea derivative by means of phosgene.

h 1 d mfi bl h th d f he 0duc 10 The complex copper and nickel compounds of the dyet T efsip E810 22m: 60:2; {gigs dgpengg 2m tlil e fact stuffs oft thelgormula 1 are obtiiried Ilily tgeatment w th ion 0 i o g F an agen y1e mg copper or me e. t is connection thgttnline sergilgreaigilg igfi f g g l gg i zz g g i a: is sometimes ladvantlageouls) to mbake 011110 aging-am su s an rox -azo-meta corn exes su 'ectin ort orox capable of being destf9yed to: all eXteBt which dffpends on ortho'-methoxy-azo-destuifs to nietalliiation a compiithe amount of image silver present due to reduction of the nied by demethylation rather than to use orthmortho'- azo linkages during treatment with a suitable dyestuffbleaching bath.

The present invention provides photographic layers suitable for the production of color images by the silver dyestufi bleaching method which are colored with azo- As examples of diam-components of the Formula 4 dyestuffs of the formula the following amines may be mentioned:

dihydroxy-azo-dyestuffs. In other respects the dyestufis and their copper and nickel complexes can be prepared in the conventional manner.

in which X represents a hydrogen or chlorine atom or S-nitro-2-amino-l-hydroxybenzene, an alkyl or sulfonic acid group, Y represents a hydrogen 4-methyl-5-nitro-2-amino-l-hydroxybenzene,

atom or an alkyl group, and m and n each represent the l-amino-2-methoxy-4-nitrobenzene, whole number 1 or 2, and in which the azo linkage and l-arnino-2-rnethoxy4-nitro-6-chlorobenzene, and the hydroxyl group in the naphthalene radical are bound 1-amino-2-methoxy-4-nitrobenzene-S-sulfonic acid.

in vicinal positions, or with complex copper or nickel compounds of these azo-dyestuffs.

The benzene radical of the formula For coupling with the diazo-compounds the following hydroxynaphthalene sulfonic acids may be used:

l-hydroxynaphthalene-4- or -5-sulfonic acid,

( X 2-hydroxynaphthalene-4-, -5-, -6-, -7- or -8-sulfonic acid,

1-hydroxynaphthalene-3:6- or 3:8-disulfonic acid, or 2-hydroxynapthalene-3z6- or -6:8-disulfonic acid.

6 As suggested by the foregoing remarks dyestuffs of the formulae o o o :HNO- i}HN-N=Ntg{som) EH )CuO contains in ortho-position to the azo linkage an alkoxY, and preferably a methoxy group, or a hydroxyl group. X may X represent a hydrogen or chlorine atom, an alkyl group f such as methyl or ethyl or a sulfonic acid group. 00 EN- -N=N \s0 In the naphthalene radical of the formula I W n OCu0 are preferably used. In these formulae X, m and n have \S a the above meanings. Certain of the dyestufis of the Formulae l, 5 and 6 are known.

HO In general it is of advantage for the layer containing the finished photographic image not to contain a metalfree dyestuff of the Formula 1, but to contain a complex heavy metal compound, preferably a complex nickel or copper compound, of such dyestutf. Such a complex metal compound may be present in the layer concerned from the outset.

The dyestuhs of the Formula 1 or their complex copper the hydroxyl group is bound in a position vicinal to the azo linkage. As further substituents the naphthalene radical contains one or two sulfonic acid groups.

The dyestuffs of the Formula 1 are advantageously made by coupling a diazo-compound of a l-amino-4- 5 nitrobenzene of the formula (4) X or nickel compounds are used in accordance with the invention in the production of colored photographic o,N NH layers, more especially gelatine layers, but also layers of I other colloids used in photography, and more especially OY as dyestuffs for purple images of original or copying materials used for color photography, that is to say, in color The photographic images produced with the dyestuffs negative materials and in color diapositives for viewing of the Formula 1 or complex metal compounds thereof by transmitted or reflected light. Thus, the layer-formare distinguished by their very good fastness to light, and ing substance colored with such a dyestuif is mixed with this fastness is not impaired by diffusion-inhibiting suba silver halide emulsion, the silver halide is sensitized in 5 stances such as guanidine, biguanides or triphenylguania suitable manner for a specific region or" the spectrum, dine present in the colored layer or in adjacent layers. and a layer of the emulsion is used, for example, as a I The following examples illustrate the invention.

component of a two-color or three-color system. Alternatively, a non-colored silver halide layer may be colored after exposure and development, and then the dye- 3 to 5 grams of the cupriferous dyestuff of the formula Example 1 1103's SIO3H S0 11 H0 8 I 0 I I OCu O O C11O stuff bleaching process is carried out. A color image are dissolved in 600 cc. of water. (The dyestufi can be obtained by the silver dyestulf bleaching process may also prepared by coupling diazotized 1-amino-2-methoxy-4- be used for a transfer process or for an imbibition nitrobenzene-S-sulfonic acid with Z-hydroxy-naphthaleneprocess. 6-sulfonic acid, reducing. the nitro-monoazo-dyestuif to As dyestuff bleaching baths there are suitable most the amino-monoazo-dyestuff, linking together the amino of the known neutral or acid, more especially strongly groups to form the urea derivatives by means of phosacid, bleaching baths that contain a solvent for silver, gene, followed by demethylating coppering.) The solusuch as thiourea, urea or a semicarbazide, and an alkali tion is added to 1000 grams of a green-sensitized silver metal halide, such as sodium or potassium chloride, bromide gelatine emulsion containing 25 to grams of bromide or iodide, or an ammonium halide. The catr silver. The quantities of dyestufi and silver bromide are alysts known for use in bleaching baths for azo-dyestutts, adjusted within the aforementioned limits depending on such as anthraquinone and its sulfonic acids or dimethyl- Whether the photographic images to be produced are inquinoxaline and also amino-hydroxyphenazines, generaltended for viewing by reflected or transmitted light and ly also accelerate the dyestuit bleaching process. depending on the thickness of the layer.

It has been observed that layers rich in silver yield 0 The colored silver bromide gela-tine emulsion is cast color images of an excellently flat gradation. Any image on the chosen support, that is to say, on paper or a film silver not required for the dyestutf bleaching process is base, as a component of a three layer material. After converted into silver halide in known manner by means being dried, the material is exposed, and the negative of an oxidizing bath in the presence of an alkali metal Silv r image is developed with a solution containing, per halide, for example, by means of potassium ferricyanide 7 liter of water, 1 gram of methyl-para-amino-phenol, 3 d potassium bro id or by mean of an a id bath grams of hydroquinone, 25 grams of sodium sulfite, containing copper sulfate and sodium chloride. Finally, grams of sodium carbonate and 1 gram of potassium the layer is fixed in known manner in a sodium thiosulhl'omldfi- Thfi develflphlg time ranges from 5 t0 7 f t bath, washed and i utes. The material is then washed in water for one The bleaching process can be further assisted by inr minute and fixed for five minutes in a bath containing, termediate washing with water, for example, by bleach Per liter of Water, 200 grams of sodium thiosulfate and ing for 10 minutes, washing for 5 minutes, bleaching 25 grams of potassium metabisulfite. The material is again for 10 minutes, washing for 5 minutes and then fixed for 5 minutes, then washed again in water for 5 completing the bleaching. The addition of a waterto 7 minutes and hardened for 5 minutes in an aqueous soluble organic solvent such as an alcohol, cetone, formaldehyde solution of 4% strength. The material is OXahe, a glycol 0f dextrose y also assist the dyestuft' again Washed for 5 minutes, and then treated for 20 bleaching process. minutes in a silver dyestuff bleaching bath which con- Instead of incorporating a metalliferous dyestuff with i per lit f ater, to 100 grams of potassium the p p material initially: a metal-free bromide, 30 to grams of thiourea, 40 to 80 cc. of hy- S uff f the Formula 1 may be 50 incorporated and 9 60 drochloric acid of 37% strength and as catalyst 1 cc. of verted into the metal complex in the material, containlng a Solution of 1% Strength of aminohydwxyphfinazina the color image- 511011 a Conversion takhs P161Ce h The material is then washed for 5 minutes. Any unconsively or even completely when the known strongly acid sumed image il i removed in a bath Co P copper sulfate solution is used as silver bleaching bath. liter, f Water, 60 grams f copper sulfate, 80 grams of However, Complexes of other heavy metals, a (35 potassium bromide and 30 cc. of hydrochloric acid of tendency t0 P P in Strongly acid media- In Such 37% strength, which converts the silver into silver 0886 that is t0 3 when the layer initially Contains bromide, which, after washing the material for about 5 such a complex or Wh n the c p is formed minutes, is removed by dissolution in a fixing bath consequently, it is preferable not 0 use a Strongly acid bath, taining 200 grams of sodium thiosulfate per liter of water.

and not to use a Silver bleaching bath Containing PPW, Finally, the material is again washed for 5 minutes and since otherwise there may finally be present, for exdried. A reversed image of pure purple tint is obtained ample, instead of the desired unitary nickel complex, which is very fast to light.

a mixture of nickel and copper complexes and/ or metal- Instead of the dyestuif of the Formula 7, there may be free dyestuff. used for purple layers the corresponding complex nickel compound or one of the cupriferous dyestuffs of the from copper ions, for example with a solution containing formulae: per liter of water, 60 grams of potassium ferricyamde,

( u (|)----Cu O l 0 I S0311 HO S 110 's (|)Cu(|) (l)-Cu-O S0311 SOGH H; H; Hogs Boss 1103 s S|O3H 1103 s I 0 0 0 I o0uo 0-Cu 0 The dyestutf of the Formula 12 is distinguished by its grams of potassium bromide, 13 grams of secondary particularly good fastness to diffusion. sodium phosphate and 6 grams of sodium sulfite. In this manner a metal-free dyestutf image is formed which has Example 2 strong indicator action in that it exhibits a blue tint in The procedure is the same as described in Example 1, alkaline media and a reddish brown tint in acid media. except that the metal-free dyestuif of the formula When the metal-free dyestulf image is after-treated with 3) 1103's S|O3H S|O3H HOaIS N=NONH-c o-HNOrr: 6H m) (')H m) is used instead of the copper compound mentioned in that a solution of nickel sulfate or nickel acetate containing example. The same result is obtained, that is to say, the 0.5 to 2% of the nickel salt, the metal-free dyestufi is conpurple tint of the complex copper compound of the dye verted in a few minutes into the nickel complex which is obtained, because in the silver dyestuff bleaching bath also has a purple color, but is slightly more reddish than containing copper sulfate and potassium bromide in acid the copper complex. This image is likewise very fast to solution the complex copper compound of the azo dye light and no longer possesses indicator characteristics. is formed immediately. What is claimed is: g

If it is desired to prevent this, the residual image silver" 1. A photographic silver halide emulsion layer for the must be treated with a silver bleaching bath that is free silver dyestufi bleaching process, which layer is. colored with a complex copper compound of an azo-dyestufi of in which m and I: each represents a whole number of at the formula the most 2.

/l l X 0 C HaQtNZN m as I L m-l OY no 2 in which X represents a member selected from the group 5. A photographic silver halide emulsion layer for the consisting of a hydrogen atom, a chlorine atom, a lower silver dyestulf bleaching process, which layer is colored alkyl group and a sulfonic acid group, Y represents a 10 with an ortho:ortho-dihydroxy-azo copper complex commember selected from the group consisting of a hydrogen pound of the formula OCu0 , in which m and it each represents a whole number of at the most 2. atom and a lower alkyl group, m and it each represents 20 A Photographic Silver halide emulsion layer for the a whole number of at the most 2, and in which the azo Silver dyestuff bleaching Process, which layer is colored linkage and the hydroxyl group in the naphthalene radical with an ortho=0rth0-dihydrOXy-aw pp p e o are bound in vicinal positions. I Pound of the formula 2. A photographic silver halide emulsion layer for the H038 silver dyestulf bleaching process, which layer is colored 2 5 I V f with an ortho:ortho-dihydroxy-azo copper complex com- 0 N=N \SO3H pound of the formula I OCu0 2 in which n represents a whole number of at the most 2.

O I H03? F G Q t 0o HN -O-HN N=N SO3H L l I .1

m oon -o, 2 in which m and n each represents a whole number of at 7. A photographic silver halide emulsion layer for the the most 2. silver dyestutt bleaching process, which layer is colored 3. A photographic silver halide emulsion layer for the with the ortho:ortho-dihydroxy-azo copper complex comsilver dyestutf bleaching process, which layer is colored pound of the formula with an ortho:ortho-dihydroxy-azo copper complex com- 8. A photographic silver halide emulsion layer for the pound of the formula silver dyestutr bleaching process, which layer is colored in which m and it each represents a whole number of at with the ortho:ortho'-dihydroxy-azo copper complex comthe most 2. pound of the formula 4. A photographic silver halide emulsion layer for the silver dyestutt bleaching process, which layer is colored 9. A photographic silver halide emulsion layer for the with an ortho:ortho'-dihydroxy-azo copper complex comsilver dyestulfv bleaching process, which layer is colored pound of the formula with the ortho:ortho-dihydroxy-azo copper complex com- 11. A photographic silver halide emulsion layer for the pound of the formula I silver dyestufi bleaching process, which layer is colored E0 3 (|)--Cu(|) )-ou---o S0311 0 V S0311 IEIOaS- 10. A photographic silver halide emulsion layer for With the orthozorthd-dihydroxy-azo copper complex comthe silver dyestufi bleaching process, which layer is 001- pound of the formula ored with the ortho:ortho'-dihydroxy-azo copper com- 12. A photographic silver halide emulsion layer for the plex compound of the formula silver dyestufif bleaching process, which layer is colored With the ortho:ortho-dihydroxy-azo copper complex compound of the formula HOQIS S|O H 03's I I (i 0 0 1 O u0 References Cited by the Examiner UNITED STATES PATENTS 1,300,616 4/19 Ives 96--57 1,305,962 6/19 Crabtree 96-57 1,940,066 12/ 33 Stusser 260148 2,294,892 12/42 Carroll et al 9699 2,304,884 12/42 Carroll et a1. 96-99 2,418,624 4/47 Chechak et a1 96-99 2,612,448 9/52 Gaspar et a1. 96-99 3,038,802 6/ 62 Keller et a1. 96-73 OTHER REFERENCES Color Index, Compound #23410, V0]. 3, 2nd Ed., 1956, page 3203.

Venkataraman: Synthetic Dyes, vol. 1, 1952, Academic Press Inc., Publishers, N.Y., pp. 557-560.

NORMAN G. TORCHIN, Primary Examiner.

HAROLD N. BURSTEIN, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,178,290 April 13, 1965 Walter Anderau It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 7 and 8, claim 3, for that portion of the formula reading:

read

same columns 7 and 8, claim 7, for that portion of the formula reading:

Signed and sealed this 28th day of September 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attestlng Officer Commissioner of Patent: 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER FOR THE SILVER DYESTUFF BLEACHING PROCESS, WHICH LAYER IS COLORED WITH A COMPLEX COPPER COMPOUND OF AN AZO-DYESTUFF OF THE FORMULA 